3 Answers
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Those of us trained in mathematics tend to interpret words like "multiply" as if a mathematical problem was being stated. However, making an argument of this sort on the basis of the word רָבָה, to cause to increase, would be a stretch. Remember that even the root meaning of the English word multiply is to make many. Given the context, the emphasis on this verse is that she has plunged herself into sorrow when she was in bliss before, not she had pain and now it would be increased.

On the other hand, it is notable that the line between pain and a strong pleasure is not distinct. For example, I enjoy a level of spiciness in my food that many people would consider painful; but there are others to whom the level of spice which I can tolerate does not seem painful at all. It is purely in the realm of speculation to try to pin down exactly what type of sensory experiences there might have been prelapsarian. A weak pain may be a pleasure, where a multiplied pain is agony.

The deciding issue is really the context. She has passed over from a state of beatitude into one that is accursed. Regardless of the exact meaning of pain, sorrow clearly would not exist in a world pronounced so profoundly good (Gen 1:4, 10, 12, 18, 21, 25, 31). The point of the narrative is to show that the blame for the sorrows of the human race rests squarely on its own shoulders.

It may be noteworthy (in addition) that neurophysiologically one highly aggravating factor to pain is anxiety. The very same verse names two compensatory strategies to ameliorate the future fears and insecurities (for the woman: desiring / for the man: ruling).

Pain they may have experienced before, but probably never to the point of threat.

(Assuming a literal interpretation): the Hebrew is actually, "Ha-ReBah" (pardon the transliteration, I don't have the right font on this machine), which I believe also translates to "increase". The same root is translated "increase" in Gen. 7:17 referring to the raising of waters in the flood:

The flood continued forty days upon the earth; and the waters increased ("Yi-ReBu"), and bore up the ark, and it rose high above the earth. (RSV)

If you take the meaning to mean, "increase", then, since going from 0 to 1 is necessarily an increase, it does not need to have the implication that there was pain before the fall.